Supporting Information for:

Transcription

1 Supporting Information for: [Ir(N^N^N)(C^N)L] + : A New Family of Luminophores Combining Tunability and Enhanced Photostability Danielle N. Chirdon, Wesley J. Transue, Husain N. Kagalwala, Aman Kaur, Andrew B. Maurer, Tomislav Pintauer and Stefan Bernhard Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania and Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania Mass Spectra Electrochemical Measurements UV-Vis Absorption Spectra Computational Models of Emission Energy Calculated Orbitals and Geometries NMR Spectra Crystallography Parameters and Data S2 S3-S4 S5-S6 S7 S8-S25 S26-S34 S35-S41 -S1-

2 Figure S1. Electrospray ionization mass spectra collected for 2a in acetonitrile (left) and methanol (right). Peak m/z values are given with black labels while assignments are made in blue. Spectra were collected with μm solutions. Figure S2. Electrospray ionization mass spectra collected for 3a in acetonitrile (left) and methanol (right). Peak m/z values are given with black labels while assignments are made in blue. Spectra were collected with μm solutions. -S2-

3 Current (μa) Current (μa) Potential (V vs SCE) Figure S3: Cyclic voltammogram of 2g showing its unique oxidation processes. The voltammogram was collected at 0.10 V/s using a three electrode system in a 0.10 M N(n-Bu) 4 PF 6 (MeCN) solution. Potentials are referenced to SCE via a ferrocene internal standard Potential (V vs Silver Wire) Figure S4: Cyclic voltammogram of model compound [Ir(tpy)(ppy)(py)](PF 6 ) 2 where py is pyridine. The second reduction which is reversible here is irreversible in all chloro compounds suggesting that the chloride may be causing the irreversibility by dissociating before or during the reduction process. A third reduction is visible for the pyridine complex as in the chlorides. The voltammogram was collected at 0.10 V/s using a three electrode system in a 0.10 M N(n-Bu) 4 PF 6 (MeCN) solution. Potentials are referenced to a silver wire pseudoreference. -S3-

4 Current (μa) Current (μa) A V/s B 1.5 V/s Potential (V vs SCE) Potential (V vs SCE) -5.0 C 0.1 V/s THF Potential (V vs SCE) Figure S5: Scan rate and solvent dependence of reductions in 2a. Cyclic voltammograms collected at (A) 0.10 V/s in MeCN, (B) 1.5 V/s in MeCN, and (C) 0.10 V/s in THF. Potentials are referenced to a ferrocene internal standard. All voltammograms were measured using 0.10 M N(n-Bu) 4 PF 6 as electrolyte and a three electrode system. -S4-

5 Figure S6: UV-vis absorption spectra for the tpy subset of compounds including 2a (green), 2b (purple), and 2c (orange). UV-vis absorption spectra for all other members of the luminophore family are shown in the background in gray. All spectra were collected at room temperature in 10μM acetonitrile solutions. Figure S7: UV-vis absorption spectra for the phenylterpyridine subset of chloro compounds including 2d (green dashes), 2e (purple dashes), and 2f (orange dashes). UV-vis absorption spectra for all other -S5-

6 members of the luminophore family are shown in the background in gray. All spectra were collected at room temperature in 10μM acetonitrile solutions. Figure S8: UV-vis absorption spectra for the cyano subset of compounds including 3a (green) and 3b (purple). UV-Vis absorption spectra for all other members of the luminophore family are shown in the background in gray. All spectra were collected at room temperature for 10μM acetonitrile solutions. -S6-

7 y = x R² = y = x R² = Figure S9: Comparison between experimental emission energy and a standard computational predictor of trends in emission: the difference in SCF energies for the triplet excited and singlet ground states calculated at the optimized triplet geometry. Linear correlations are identified for subsets of the luminophore family (green=[ir(phtpy)(c^n)cl](pf 6 ) and blue=[ir(tpy)(c^n)cl](pf 6 )). Figure S10: Correlations between experimental emission energy and two common computational predictors which model trends in emission by taking the difference between energies calculated for particular orbitals. The LUMO-HOMO model represented in blue diamonds involves subtracting the energies of the HOMO and LUMO calculated at the optimized singlet geometry. The HSOMO-HOMO model shown with red squares is based on the difference in the energies of the HOMO at the optimized singlet geometry and the HSOMO at the optimized triplet excited state geometry. -S7-

8 DFT Results for 2a SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S8-

9 Singlet Optimized Coordinates for 2a: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S9-

10 DFT Results for 2b SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S10-

11 Singlet Optimized Coordinates for 2b: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S11-

12 DFT Results for 2c SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S12-

13 Singlet Optimized Coordinates for 2c: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S13-

14 DFT Results for 2d SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S14-

15 Singlet Optimized Coordinates for 2d: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S15-

16 DFT Results for 2e SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S16-

17 Singlet Optimized Coordinates for 2e: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S17-

18 DFT Results for 2f SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S18-

19 Singlet Optimized Coordinates for 2f: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S19-

20 DFT Results for 2g SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S20-

21 Singlet Optimized Coordinates for 2g: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S21-

22 DFT Results for 3a SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S22-

23 Singlet Optimized Coordinates for 3a: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S23-

24 DFT Results for 3b SCF Energy: a.u. Frontier Orbitals: Orbital Energy / ev LUMO HOMO HOMO S24-

25 Singlet Optimized Coordinates for 3b: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S25-

26 -S26- Figure S11: 1 H NMR spectrum collected for 2a in acetone-d 6 using a 300 MHz spectrometer. Residual solvent peaks are visible at 3.4 and 1.1 ppm.

27 -S27- Figure S12: 1 H NMR spectrum collected for 2b in acetone-d 6 using a 300 MHz spectrometer.

28 -S28- Figure S13: 1 H NMR spectrum collected for 2c in acetone-d 6 using a 300 MHz spectrometer.

29 -S29- Figure S14: 1 H NMR spectrum collected for 2d in acetone-d 6 using a 300MHz spectrometer.

30 -S30- Figure S15: 1 H NMR Spectrum for 2e collected in acetone-d 6 using a 300 MHz spectrometer.

31 -S31- Figure S16: 1 H NMR spectrum collected for 2f in acetone-d 6 using a 300MHz spectrometer.

32 -S32- Figure S17: 1 H NMR spectrum of 2g collected in acetone-d 6 using a 300 MHz spectrometer.

33 -S33- Figure S18: 1 H NMR spectrum collected for 3a in acetone-d 6 using a 300 MHz spectrometer.

34 -S34- Figure S19: 1 H NMR spectrum collected for 3b in acetone-d 6 using a 300 MHz spectrometer.

35 Table S1. X-ray Crystallographic Data and Parameters for [Ir(tpy)(MeO-mppy)Cl](PF 6 ) [Ir(tpy)(MeO-mppy)Cl](PF 6 ) Formula C 28 H 23 ClF 6 IrN 4 OP Color Yellow Shape Plates Formula Weight Crystal System Triclinic Space Group P-1 Temp (K) 150 Cell Constants a, Å (2) b, Å (4) c, Å (4) α, deg (10) β, deg (10) γ, deg (10) V, Å (8) Formula units/unit cell 2 Dcal'd, gcm Absorption coefficient, mm F(000) 832 Diffractometer Bruker Smart ApexII Radiation, graphite monochr. Mo K ʎ (ʎ = Å) Crystal size, mm 0.34 x 0.22 x 0.11 θ range, deg 1.5< θ <32.7 Range of h,k,l ±12, ±23, ±24 Reflections collected/unique 31772/12005 Rint Refinement Method Full Matrix Least-Squares on F2 Data/Restraints/Parameters 12005/0/446 GOF on F Final R indices [I>2σ(I)] R1=0.025 wr2=0.089 R indices (all data) R1=0.027 wr2= Max. Resid. Peaks (e*å -3 ) 2.32 and Table S2: Fractional Atomic Coordinates and Isotropic or Equivalent Isotropic Displacement Parameters (Å 2 ) for [Ir(tpy)(MeO-mppy)Cl](PF 6 ). x y z U iso */U eq Ir (2) (2) (2) (4) Cl (9) (5) (5) (12) P (12) (5) (5) (16) N (3) (16) (15) (4) N (3) (15) (14) (4) F (3) (14) (16) (5) -S35-

36 C (3) (17) (16) (4) N (3) (16) (13) (4) F (3) (14) (15) (5) C (4) (2) (17) (5) H * C (3) (19) (16) (4) C (4) (2) (17) (5) H * C (4) (2) (19) (6) H * C (4) (2) (19) (7) H * C (4) (3) (2) (7) H * C (3) (18) (17) (4) C (3) (18) (17) (4) C (4) (2) (3) (7) H * C (4) (2) (2) (5) H * C (4) (2) (2) (6) H * C (3) (18) (16) (4) C (4) (2) (18) (5) C (4) (2) (18) (5) H * C (4) (2) (18) (5) H * C (3) (18) (15) (4) C (4) (2) (2) (5) O (3) (2) (17) (5) C (4) (2) (2) (6) H * C (3) (18) (17) (4) H * C (4) (2) (2) (6) H * C (4) (2) (3) (6) H13A * H13B * H13C * C (5) (3) (2) (9) H12A * H12B * H12C * F (3) (17) (2) (7) -S36-

37 F (5) (18) (16) (8) F (4) (17) (2) (8) F (5) (2) (16) (8) N (3) (15) (13) (4) C (4) (18) (17) (5) C (5) (2) (2) (7) H * C (4) (2) (17) (5) H * C (4) (2) (2) (6) H * C (4) (2) (2) (7) H * C (6) (4) (3) (9) C (7) (4) (4) (16) H29A * H29B * H29C * N (6) (3) (3) (9) O (17) (8) (11) (9) H2A * C (17) (7) (11) (7) H38A * H38B * Table S3: Atomic Displacement Parameters (Å 2 ) for [Ir(tpy)(MeO-mppy)Cl](PF 6 ). U 11 U 22 U 33 U 12 U 13 U 23 Ir (5) (5) (5) (3) (3) (4) Cl (3) (3) (3) (2) (2) (3) P (4) (3) (3) (3) (3) (2) N (9) (9) (9) (7) (7) (7) N (9) (8) (8) (7) (7) (7) F (13) (8) (12) (8) (10) (8) C (10) (10) (10) (8) (8) (8) N (9) (9) (8) (7) (7) (7) F (12) (8) (12) (8) (10) (8) C (12) (12) (10) (10) (9) (9) C (10) (11) (10) (8) (8) (9) C (12) (12) (10) (10) (9) (9) C (13) (14) (12) (11) (10) (11) C (16) (15) (11) (12) (10) (10) C (16) (16) (12) (13) (11) (12) C (12) (10) (11) (8) (9) (9) C (10) (11) (11) (8) (8) (9) C (14) (14) (2) (11) (13) (14) -S37-

38 C (11) (13) (15) (10) (10) (12) C (14) (12) (14) (10) (12) (11) C (10) (10) (10) (8) (8) (8) C (12) (14) (11) (10) (9) (10) C (12) (12) (11) (10) (10) (10) C (13) (14) (12) (11) (10) (11) C (10) (9) (9) (8) (8) (8) C (13) (12) (13) (10) (10) (10) O (13) (15) (12) (12) (11) (12) C (15) (13) (17) (12) (14) (13) C (11) (10) (10) (8) (8) (8) C (15) (13) (16) (11) (13) (12) C (15) (14) (18) (12) (14) (13) C (19) (3) (17) (18) (15) (18) F (13) (11) (18) (10) (12) (11) F (2) (11) (11) (13) (13) (9) F (16) (11) (2) (11) (14) (12) F (2) (15) (11) (15) (13) (11) N (9) (9) (8) (7) (7) (7) C (12) (10) (10) (9) (9) (8) C (18) (14) (13) (12) (12) (11) C (12) (12) (10) (9) (9) (9) C (16) (12) (13) (11) (12) (10) C (15) (15) (13) (12) (11) (11) C (2) (3) (2) (18) (16) (19) C (3) (3) (3) (2) (2) (2) N (2) (2) (2) (18) (17) (18) O (14) (9) 0.44 (2) (9) (14) (12) C (13) (6) 0.37 (2) (7) (13) (10) Table S4: Bond Lengths in [Ir(tpy)(MeO-mppy)Cl](PF 6 ) (Å)* Ir1 N (2) C6 C (3) Ir1 C (2) C3 O (3) Ir1 N (2) C3 C (4) Ir1 N (2) C5 C (4) Ir1 N (2) C5 H Ir1 Cl (6) C4 H P1 F (2) C10 C (4) P1 F (2) C10 C (4) P1 F (2) C10 C (4) P1 F (3) O1 C (4) P1 F (3) C9 C (4) P1 F (2) C9 H N3 C (3) C11 H S38-

39 N3 C (3) C8 H N1 C (3) C13 H13A N1 C (3) C13 H13B C7 C (4) C13 H13C C7 C (3) C12 H12A N2 C (3) C12 H12B N2 C (3) C12 H12C C2 C (3) N4 C (3) C2 C (4) N4 C (3) C2 H C24 C (4) C18 C (3) C26 C (5) C18 C (4) C26 C (5) C14 C (4) C26 H C14 H C28 C (4) C17 C (5) C28 H C17 H C25 H C15 C (5) C27 H C15 H C30 N (6) C16 H C30 C (7) C23 C (4) C29 H29A C23 C (4) C29 H29B C19 C (4) C29 H29C C21 C (5) O2 C (16) C21 C (5) O2 H2A C21 H C38 C38 i 1.42 (2) C20 H C38 H38A C22 H C38 H38B C6 C (3) * All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Table S5: Bond Angles in [Ir(tpy)(MeO-mppy)Cl](PF 6 ) ( )* N3 Ir1 C (9) C23 C22 H N3 Ir1 N (9) C5 C6 C (2) C1 Ir1 N (9) C5 C6 C (2) N3 Ir1 N (9) C1 C6 C (2) C1 Ir1 N (9) O1 C3 C (2) N4 Ir1 N (10) O1 C3 C (2) N3 Ir1 N (8) C4 C3 C (2) C1 Ir1 N (9) C4 C5 C (2) N4 Ir1 N (8) C4 C5 H S39-

40 N2 Ir1 N (9) C6 C5 H N3 Ir1 Cl (7) C5 C4 C (2) C1 Ir1 Cl (7) C5 C4 H N4 Ir1 Cl (6) C3 C4 H N2 Ir1 Cl (6) C2 C1 C (2) N1 Ir1 Cl (6) C2 C1 Ir (18) F4 P1 F (2) C6 C1 Ir (17) F4 P1 F (15) C9 C10 C (3) F3 P1 F (15) C9 C10 C (3) F4 P1 F (18) C11 C10 C (3) F3 P1 F (17) C3 O1 C (2) F2 P1 F (14) C8 C9 C (3) F4 P1 F (17) C8 C9 H F3 P1 F (17) C10 C9 H F2 P1 F (16) N1 C11 C (2) F5 P1 F (15) N1 C11 H F4 P1 F (15) C10 C11 H F3 P1 F (14) C9 C8 C (2) F2 P1 F (13) C9 C8 H F5 P1 F (16) C7 C8 H F6 P1 F (13) C10 C13 H13A C23 N3 C (2) C10 C13 H13B C23 N3 Ir (17) H13A C13 H13B C19 N3 Ir (17) C10 C13 H13C C11 N1 C (2) H13A C13 H13C C11 N1 Ir (17) H13B C13 H13C C7 N1 Ir (17) O1 C12 H12A N1 C7 C (2) O1 C12 H12B N1 C7 C (2) H12A C12 H12B C8 C7 C (2) O1 C12 H12C C14 N2 C (2) H12A C12 H12C C14 N2 Ir (19) H12B C12 H12C C18 N2 Ir (16) C28 N4 C (2) C1 C2 C (2) C28 N4 Ir (18) C1 C2 H C24 N4 Ir (16) C3 C2 H N4 C24 C (3) N2 C18 C (3) N4 C24 C (2) N2 C18 C (2) C25 C24 C (3) C17 C18 C (2) C25 C26 C (3) N2 C14 C (3) C25 C26 H N2 C14 H C27 C26 H C15 C14 H N4 C28 C (3) C16 C17 C (3) N4 C28 H C16 C17 H C27 C28 H C18 C17 H C26 C25 C (3) C16 C15 C (3) C26 C25 H S40-

41 C16 C15 H C24 C25 H C14 C15 H C26 C27 C (3) C15 C16 C (3) C26 C27 H C15 C16 H C28 C27 H C17 C16 H N5 C30 C (5) N3 C23 C (2) C30 C29 H29A N3 C23 C (2) C30 C29 H29B C22 C23 C (2) H29A C29 H29B N3 C19 C (2) C30 C29 H29C N3 C19 C (2) H29A C29 H29C C20 C19 C (2) H29B C29 H29C C22 C21 C (3) C38 O2 H2A C22 C21 H C38 i C38 O (11) C20 C21 H C38 i C38 H38A C21 C20 C (3) O2 C38 H38A C21 C20 H C38 i C38 H38B C19 C20 H O2 C38 H38B C21 C22 C (3) H38A C38 H38B C21 C22 H * All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. i Symmetry code: x+1, y+1, z+1. -S41-